CN106698638A - Catalyst adding optimization control method for ozone catalytic-oxidation process - Google Patents
Catalyst adding optimization control method for ozone catalytic-oxidation process Download PDFInfo
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- CN106698638A CN106698638A CN201710012426.2A CN201710012426A CN106698638A CN 106698638 A CN106698638 A CN 106698638A CN 201710012426 A CN201710012426 A CN 201710012426A CN 106698638 A CN106698638 A CN 106698638A
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- ozone
- catalyst
- concentration
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- detector
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 238000005457 optimization Methods 0.000 title abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 238000006385 ozonation reaction Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002815 homogeneous catalyst Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 hydroxyl radical free radical Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 3
- 241000264877 Hippospongia communis Species 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002894 chemical waste Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/326—Lamp control systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/23—O3
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a catalyst adding optimization control method for an ozone catalytic-oxidation process, relates to an optimization method for removing organic pollutants in water of an ozone catalytic-oxidation process and belongs to the field of water treatment. The method aims at solving the problem that a catalyst added to an existing ozone catalytic-oxidation process difficultly adapts to water quality, water amount and water temperature change and accordingly the ozone utilization rate is low or a large amount of catalyst is left and comprises the steps that at least one liquid-state ozone detector is arranged on a water outlet pipeline of an ozone contact oxidation system or at least one gaseous-state ozone detector is arranged on a tail gas pipeline of the ozone contact oxidation system a concentration signal output by the ozone detector is received by using a controller, and an execution signal is analyzed and output to a catalyst adding device according to the signal, and the catalyst adding amount increase/decrease is controlled in real time so as to obtain optimal adding amount. The catalyst adding optimization control method has the advantages of being simple in operation, low in cost and capable of improving the ozone utilization rate by 10%-50%, can be popularized and applied in various scales of project applications and is mainly used for treating water containing organic pollutants.
Description
Technical field
The present invention relates to water treatment field, and in particular to added certainly for the catalyst optimization in catalytic ozonation technique
Dynamic control.
Background technology
In recent years, ozonation technology is widely used in the removal of persistent organic pollutants in water, including removal is drunk
In water and sewage the new organic pollution of difficult degradation such as incretion interferent, medicine and personal-care supplies, agricultural chemicals etc. and
The industrial wastewater of difficult degradation such as coking chemical waste water, organic chemical waste water etc..In order to increase ozone oxidation organic matter efficiency, generally add
Catalyst produces hydroxyl radical free radical to be aoxidized to accelerate ozone decomposed.The research in laboratory has been demonstrated to efficient catalytic ozone
The catalyst or catalytic way for aoxidizing organic pollution have homogeneous catalyst such as hydrogen peroxide, metal ion etc., heterogeneous catalysis
Agent such as carbon material catalyst, metal oxide, metal hydroxides, ceramic honey comb, load ceramic honey comb etc. and external energy
Source is catalyzed such as ultraviolet radiation, ultrasonic radiation.
In actual applications using catalyst dosing method and dosage often rule of thumb in the following way：If adopting
With homogeneous catalyst, the leading portion in ozone contact room adds catalyst, and the dosage of catalyst is with the dosage of ozone by catalysis
Agent is added with the reaction quantitative relation of ozone, such as O3/H2O2Technique, H2O2Dosage be H by both reaction quantitative relations2O2
With O3Mol ratio=1:2 add, and the dosage of catalyst lacks preferably and optimizes.
In fact, due to there are a large amount of organic principles in the water body background by ozone oxidation, these organic matter one side energy
Enough quick consumption ozone, i.e., realize effective utilization of ozone by the direct oxidation of ozone；On the other hand ozone point can be formed
Solution produces the chain reaction of hydroxyl radical free radical, and the free radical yield of chain reaction close to 100%, much larger than catalyst ozone point
The yield of solution is 30 ~ 80%.Due to a large amount of radical chain reactions that background organic principle in water exists and occurs, ozone catalytic oxygen
Catalyst functions only as inducing ozone and decomposes the effect for producing hydroxyl radical free radical in chemical industry skill, although can accelerate dividing for ozone
Solution, but the contribution to the free radical yield of ozone decomposed is faint.
Therefore, adding for catalyst needs optimization in catalytic ozonation technique：On the one hand, adding can't excessively cause
The oxidability of hydroxyl radical free radical increases, and the direct oxidation ability of ozone can be weakened on the contrary, while a large amount of of catalyst can be caused
Residue, influences next stage unit for treating water, such as in O3/H2O2Substantial amounts of H in technique2O2It is remaining；According to the difference for being subject to processing water quality,
Should select that different catalyst, catalyst add position and dosage is also required to optimization, on the other hand, add that I haven't seen you for ages and cause and be smelly
Oxygen decomposition rate is slower, in water or tail gas residual ozone concentration raise, causing the utilization ratio of ozone reduces, cause ozone dirt
Dye.
In sum, it is necessary to according to water quality situation and the actual oxidability of ozone, invention optimization catalytic ozonation technique
The method of the dosage of middle catalyst.
The content of the invention
The invention aims to catalyst amountses in solving existing catalytic ozonation technology blindly, it is impossible to efficiently
Using the problem of ozone oxidation ability, and a kind of catalyst optimization for catalytic ozonation technique is provided and adds controlling party
Method.
Catalyst optimization adding control method for catalytic ozonation technique is completed according to the following steps：In ozone
Liquid ozone detector/setting on the exhaust pipe of O3 contacted oxidation system is set on the outlet conduit of catalytic oxidation system
Gaseous ozone detector, it is above-mentioned at least provided with one；The concentration signal that ozone detector is exported, and root are received with a controller
According to the signal analysis and execution signal is exported in catalyst throwing device, control increases/reduce the dosage of catalyst in real time
To obtain optimum ad dition amount.
Advantage of the present invention：The present invention optimizes catalytic ozonation technique using in water with residual ozone concentration in tail gas
Using the optimization method can adapt to the change of the conditions such as water quality, water, water temperature, it is to avoid the useless consumption of ozone, ozone is realized
Efficient utilization.The method is simple to operate, inexpensive, it is possible to increase ozone utilization rate 10% ~ 50%, can be in the work of each scale
Popularization and application in Cheng Yingyong.
Brief description of the drawings
Fig. 1 is the catalyst optimization adding control method for catalytic ozonation technique described in specific embodiment one
Realize the schematic diagram of device.
Fig. 2 is the catalyst optimization adding control method for catalytic ozonation technique described in specific embodiment two
Realize the schematic diagram of device.
Specific embodiment
Specific embodiment one：Present embodiment is to add controlling party for the catalyst optimization of catalytic ozonation technique
The implementation method of method, is specifically realized by the following steps：The water injection of ozone catalysis oxidation of pending organic pollution is connect
Touch in room, liquid ozone detector is set in catalytic ozonation contact chamber exit, receiving ozone with a controller detects
The concentration signal of device output, and according to the signal analysis and execution signal is exported in catalyst throwing device, control increases in real time
Greatly/reduce the dosage of catalyst to obtain optimum ad dition amount.The optimization method can adapt to the conditions such as water quality, water, water temperature
Change, it is to avoid the useless consumption of ozone, realize the efficient utilization of ozone.The method is simple to operate, inexpensive, it is possible to increase
Ozone utilization rate 10% ~ 50%, can be applicable in the engineer applied of each scale.
With reference to Fig. 1, the device bag of catalytic ozonation contact chamber and optimization ozonation technology described in present embodiment
Include water inlet（1）, delivery port（2）, ozone contact room（3）, ozone inlet（4）, ozone outlet（5）, ozone detector
（6）, controller（7）, dosing pump（8）, homogeneous catalyst fluid reservoir（9）, in ozone contact room（3）Bottom centre sets water inlet
（1）, in ozone contact room（3）Side wall upper part sets delivery port（2）, in ozone contact room（3）Ozone is set at top center to go out
Gas port（5）, in delivery port（2）Upper perforate connects probe tube connection ozone detector（6）, the connection control of ozone detector output signal
Device（7）, controller（7）Output order gives dosing pump（8）, it is smelly that force (forcing) pump draws liquid catalyst input from catalyst stock solution tank
Oxygen contact chamber（3）In.
Operation principle：By the water of pending Organic Pollution by water inlet（1）Inject the smelly of O3 catalytic oxidation contact chamber
Oxygen contact chamber（3）In, ozone passes through ozone inlet duct（4）Add into ozone contact room（3）In, the dosage of ozone is adjusted
To 0.1mg/mgTOC ~ 100mg/mgTOC, while opening ozone detector（6）Ozone concentration, controller in detection solution（7）Receive
Collection ozone detector（6）Signal and process：Ozone detector（6）Liquid ozone concentration in the outlet of detection>During 0.2 mg/L,
Increase liquid catalyst dosage；Ozone detector（6）The liquid ozone concentration of detection<During 0.1 mg/L, liquid catalyst is reduced
Dosage；The optimum ad dition amount of catalyst maintains 0.1 ~ 0.2mg/L to cause that O3 contacted oxidation system goes out Measuring Ozone Concentration in Water.
Specific embodiment two：With reference to Fig. 2, catalytic ozonation contact chamber and optimization ozone oxygen described in present embodiment
The device of chemical industry skill includes water inlet（1）, delivery port（2）, ozone contact room（3）, ozone inlet（4）, ozone outlet
（5）, ozone detector（6）, controller（7）, ultraviolet irradiation device（8）, in ozone contact room（3）Bottom centre sets water inlet
（1）, in ozone contact room（3）Side wall upper part sets delivery port（2）, in ozone contact room（3）Ozone is set at top center to go out
Gas port（5）, in delivery port（2）Upper perforate connects probe tube connection ozone detector（6）, the connection control of ozone detector output signal
Device（7）, controller（7）Output order gives ultraviolet irradiation device（8）, control the size and keying shape of the input power of uviol lamp
State.
Operation principle：By the water of pending Organic Pollution by water inlet（1）Inject the smelly of O3 catalytic oxidation contact chamber
Oxygen contact chamber（3）In, ozone passes through ozone inlet duct（4）Add into ozone contact room（3）In, the dosage of ozone is adjusted
To 0.1mg/mgTOC ~ 100mg/mgTOC, while opening ozone detector（6）Ozone concentration, controller in detection solution（7）Receive
Collection ozone detector（6）Signal and process：Ozone detector（6）Liquid ozone concentration in the outlet of detection>During 0.2 mg/L,
Increase ultraviolet irradiation device（8）The unlatching quantity of input power or uviol lamp；Ozone detector（6）The liquid ozone concentration of detection
<During 0.1 mg/L, ultraviolet irradiation device is reduced（8）The unlatching quantity of input power or uviol lamp；Ultraviolet irradiation device it is optimal
Input power maintains 0.1 ~ 0.2mg/L to cause that O3 contacted oxidation system goes out Measuring Ozone Concentration in Water.
Claims (6)
1. a kind of catalyst for catalytic ozonation technique adds autocontrol method, it is characterised in that utilize ozone contact
Unemployed ozone concentration is the optimum ad dition amount for indicating state modulator catalyst in oxidative system, and the control method is to pass through
What following steps were completed：Liquid ozone detector/in ozone contact oxygen is set on the outlet conduit of O3 contacted oxidation system
Gaseous ozone detector is set on the exhaust pipe of change system, it is above-mentioned at least provided with one；Ozone is received with a controller to examine
The concentration signal of device output is surveyed, and according to the signal analysis and exports execution signal in catalyst throwing device, control is in real time
Increase/reduce the dosage of catalyst to obtain optimum ad dition amount.
2. a kind of catalyst for catalytic ozonation technique according to claim 1 adds autocontrol method, its
It is characterised by that controller is realized using the concentration signal control chemicals feed pump that ozone detector is exported by following dependency relation：
The liquid ozone concentration of detection>During 0.2 mg/L, increase catalyst dosage；The liquid ozone concentration of detection<During 0.1 mg/L, drop
Low catalyst dosage；The optimum ad dition amount of catalyst for cause O3 contacted oxidation system go out Measuring Ozone Concentration in Water maintain 0.1 ~
0.2mg/L。
3. a kind of catalyst for catalytic ozonation technique according to claim 1 adds autocontrol method, its
It is characterised by that controller is realized using the concentration signal control chemicals feed pump that ozone detector is exported by following dependency relation：
The gaseous ozone concentration of detection>0.2 g/m3When, increase catalyst dosage；The gaseous ozone concentration of detection<0.1 g/m3When, drop
Low catalyst dosage；The optimum ad dition amount of catalyst to cause that ozone concentration maintains 0.1 in O3 contacted oxidation system tail gas ~
0.2 g/m3。
4. a kind of catalyst for catalytic ozonation technique according to claim 1 adds autocontrol method, its
Described catalyst is characterised by for homogeneous catalyst, including hydrogen peroxide, peroxy-monosulfate, metal ion, ultraviolet radiation,
The composite catalyst of one or more mixing of ultrasonic radiation；Described metal ion is Fe2+、Mn2+；Described ultraviolet light spoke
Intensity is penetrated for 0.1 mW ~ 100 W；Described ultrasonic radiation intensity is 0.1 W ~ 10 kW.
5. a kind of catalyst for catalytic ozonation technique according to claim 1 adds autocontrol method, its
It is characterised by that described O3 contacted oxidation system is ozone contact tank, ozone contact tower, ozone contact tank and ozone contact post.
6. a kind of catalyst for catalytic ozonation technique according to claim 1 adds autocontrol method, its
It is characterised by that described controller also additionally considers concentration, ultraviolet radiation facility technical parameter, the ultrasonic spoke of the catalyst
Injection device technical parameter controlling catalyst dosage in real time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012426.2A CN106698638A (en) | 2017-01-09 | 2017-01-09 | Catalyst adding optimization control method for ozone catalytic-oxidation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710012426.2A CN106698638A (en) | 2017-01-09 | 2017-01-09 | Catalyst adding optimization control method for ozone catalytic-oxidation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106698638A true CN106698638A (en) | 2017-05-24 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710012426.2A Pending CN106698638A (en) | 2017-01-09 | 2017-01-09 | Catalyst adding optimization control method for ozone catalytic-oxidation process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225308A (en) * | 2020-10-09 | 2021-01-15 | 江苏南大华兴环保科技股份公司 | Device and method for treating biotoxic wastewater based on ozone oxidation technology |
| CN115010239A (en) * | 2022-06-28 | 2022-09-06 | 哈尔滨工业大学（深圳） | Method and system for treating wastewater by ozone-advanced oxidation |
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| CN102276095A (en) * | 2011-07-14 | 2011-12-14 | 哈尔滨工业大学 | Method for degrading organic pollutants in water by gradient ozone catalytic oxidation |
| CN102491563A (en) * | 2011-12-22 | 2012-06-13 | 哈尔滨工业大学 | Three-stage catalysis ozone oxidation water purifying device |
| CN104591370A (en) * | 2015-01-21 | 2015-05-06 | 哈尔滨工业大学 | Water treatment method with combined hydrogen peroxide and persulfates to catalyze ozone |
-
2017
- 2017-01-09 CN CN201710012426.2A patent/CN106698638A/en active Pending
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| CN1284933A (en) * | 1998-11-05 | 2001-02-21 | 旭化成工业株式会社 | Water treating method |
| CN102145932A (en) * | 2011-05-19 | 2011-08-10 | 哈尔滨工业大学 | Water treatment method for catalyzing ozone by using persulfate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225308A (en) * | 2020-10-09 | 2021-01-15 | 江苏南大华兴环保科技股份公司 | Device and method for treating biotoxic wastewater based on ozone oxidation technology |
| CN112225308B (en) * | 2020-10-09 | 2021-05-18 | 江苏南大华兴环保科技股份公司 | Device and method for treating biotoxic wastewater based on ozone oxidation technology |
| CN115010239A (en) * | 2022-06-28 | 2022-09-06 | 哈尔滨工业大学（深圳） | Method and system for treating wastewater by ozone-advanced oxidation |
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Application publication date: 20170524 |